Marco T. Grassi

Copper, lead and cadmium loads and behavior in urban stormwater runoff in Curitiba, Brazil

We investigate the presence and behavior of Cu, Pb, and Cd in runoff waters from a residential area located in the city of Curitiba, Brazil. Samples were collected in twenty-one stormwater events in an intermediate traffic way located in the Bacacheri watershed. Metal concentrations were similar to range values compiled worldwide and followed the order: Pb>Cu>>Cd. Unit loads were estimated to the watershed, which cover an area of 30 km2, revealing values of 1520, 950, 25 kg for Pb, Cu, and Cd, respectively. Among the three metals, lead showed the greatest affinity for the suspended solids (82%) followed by Cd (66%) and Cu (48%). Meanwhile, an association of the metals with the organic matter in the dissolved phase, following the order Cu>Pb>Cd. Metal loads and behavior in urban runoff also depends on factors such as the first flush and the dry period preceding a storm event.

Distribution and origin of polycyclic aromatic hydrocarbons in surface sediments from an urban river basin at the Metropolitan region of Curitiba, Brazil.

The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in surface sediment samples from nine sites located at the Iguaçu River Basin in the Metropolitan Region of Curitiba, Brazil to evaluate their distribution and sources. The total concentration of the PAHs was greater for sediments from highly urbanized areas, while the sediments from the Iraí Environmental Protection Area (Iraí EPA) showed significantly low concentrations. The sediments from the Iguaçu and Barigui rivers were classified as highly contaminated, while those from the Cercado and Curralinho rivers were classified as moderately contaminated. The predominance of PAHs containing two to four aromatic rings in most of the samples suggested the direct input of raw sewage into the water resources evaluated. Benzo[g,h,i]perylene, dibenzo[a,h]anthracene and indeno[1,2,3-cd]pyrene were predominant in sediments from the areas under the greatest urban and industrial development. The correlation between thermodynamic stability and the kinetics of evolution presented by the isomeric pairs indicated that combustion is the predominant source of PAHs in the sediments because the combustion of fossil fuels affected most of the points evaluated, followed by combustion of biomass and eventually combustion of oil product inputs. In general, the results showed that areas under strong urban influence, as well as the Iraí EPA, receive contributions of PAHs from similar sources.

Partition of copper between dissolved and particulate phases using aluminum oxide as an aquatic model phase: effects of pH, solids and organic matter

A adsorcao de cobre sobre oxido de aluminio modificado, em meio aquoso, foi avaliada neste trabalho. A modificacao do Al2O3 foi realizada atraves da adsorcao de acido humico comercial a sua superficie. A adsorcao do cobre foi governada por fatores tais como pH, teores de materia orgânica (particulada e dissolvida) e concentracao do material solido. A adsorcao do metal aumentou com o aumento do pH e igualmente com o aumento nos teores de materia orgânica na fase particulada. O coeficiente de particao (Kd) do cobre diminuiu com o aumento na concentracao do material solido. Os valores de Kd foram sempre mais elevados na regiao de pH neutro e decresceram tanto para regioes mais baixas quanto mais elevadas de pH. Tambem foi observado um decrescimo na adsorcao do cobre quando a concentracao de materia orgânica dissolvida foi aumentada.

A preliminary nationwide survey of the presence of emerging contaminants in drinking and source waters in Brazil

This is the first nationwide survey of emerging contaminants in Brazilian waters. One hundred drinking water samples were investigated in 22 Brazilian state capitals. In addition, seven source water samples from two of the most populous regions of the country were evaluated. Samples were collected from June to September of 2011 and again during the same period in 2012. The study covered emerging contaminants of different classes, including hormones, plasticizers, herbicides, triclosan and caffeine. The analytical method for the determination of the compounds was based on solid-phase extraction followed by analysis via liquid chromatography electrospray triple-quadrupole mass spectrometry (LC-MS/MS). Caffeine, triclosan, atrazine, phenolphthalein and bisphenol A were found in at least one of the samples collected in the two sampling campaigns. Caffeine and atrazine were the most frequently detected substances in both drinking and source water. Caffeine concentrations in drinking water ranged from 1.8ngL-1 to values above 2.0μgL-1 while source-water concentrations varied from 40ngL-1 to about 19μgL-1. For atrazine, concentrations were found in the range from 2.0 to 6.0ngL-1 in drinking water and at concentrations of up to 15ngL-1 in source water. The widespread presence of caffeine in samples of treated water is an indication of the presence of domestic sewage in the source water, considering that caffeine is a compound of anthropogenic origin.

Identification of copper sources in urban surface waters using the principal component analysis based on aquatic parameters

The goal of this work was to identify the sources of copper loads in surface urban waters using principal component analysis under the aquatic parameters data evaluation approach. Water samples from the Irai and Iguacu rivers were collected monthly during a 12-month period at two points located upstream and downstream of a metropolitan region. pH, total alkalinity, dissolved chloride, total suspended solids, dissolved organic matter, total recoverable copper, temperature, and precipitation data provided some reliable information concerning the characteristics and water quality of both rivers. Principal component analysis indicated seasonal and spatial effects on copper concentration and loads in both environments. During the rainy season, non-point sources such as urban run-off are believed to be the major source of copper in both cases. In contrast, during the lower precipitation period, the discharge of raw sewage seems to be the primary source of copper to the Iguacu River, which also exhibited higher total metal concentrations.

Healthy environment — indoor air quality of Brazilian elementary schools nearby petrochemical industry

The mitigation of pollution released to the environment originating from the industrial sector has been the aim of all policy-makers and its importance is evident if the adverse health effects on the world population are considered. Although this concern is controversial, petroleum refinery has been linked to some adverse health effects for people living nearby. Apart from home, school is the most important indoor environment for children and there is increasing concern about the school environment and its impact on health, also in developing countries where the prevalence of pollution is higher. As most of the children spend more than 40% of their time in schools, it is critical to evaluate the pollution level in such environment. In the metropolitan region of Curitiba, South Brazil, five schools nearby industries and highways with high density traffic, were selected to characterize the aerosol and gaseous compounds indoor and outdoor of the classrooms, during 2009-2011. Size segregated aerosol samples were collected for analyses of bulk and single particle elemental profiles. They were analyzed by electron probe X-ray micro-analysis (EPXMA), and by energy-dispersive X-ray fluorescence (EDXRF), to investigate the elemental composition of individual particles and bulk samples. The concentrations of benzene, toluene, ethylbenzene, and xylene (BTEX); NO2; SO2; acetic acid; and formic acid were assessed indoor and outdoor using passive diffusion tubes. BTEX were analyzed by GC-MS and other collected gasses by ion chromatography. Individual exposition of BTEX was assessed by personal passive diffusion tubes. Results are interpreted separately and as a whole with the specific aim of identifying compounds that could affect the health of the scholars. In view of the chemical composition and size distribution of the aerosol particles, local deposition efficiencies in the childrens respiratory systems were calculated, revealing the deposition of particles at extrathoracic, tracheobronchial and pulmonary levels.

Remoção dos hormônios 17β-estradiol e 17α-etinilestradiol de soluções aquosas empregando turfa decomposta como material adsorvente

This paper describes the adsorption of 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) from aqueous solution by decomposed peat. The peat presented a good adsorption process, close to 76.2% for E2 removal and approximately 55.0% for EE2. Moreover, the results indicated a probable multi-layered process. Adsorption isotherms were well fitted by Freundlich model. The data were evaluated considering the pseudo-first-order and pseudo-second-order approaches, being the second more significant mechanism in the rate-controlling step. Thermodynamic data revealed that hormones adsorption onto peat is spontaneous under the employed experimental conditions. The results confirmed the potential of this adsorbent to be employed for effluents treatment.

Effects of ecologically relevant concentrations of cadmium in a freshwater fish

Sub-chronic effects of ecologically relevant concentrations of cadmium (Cd) were evaluated in the catfish Rhamdia quelen. The fish were exposed to Cd (0, 0.1, 1, 10 and 100μgL(-1)) for 15 days. Bioconcentration was observed in the liver of fish exposed to 10 and 100μgL(-1) of cadmium. The liver glutathione S-transferase activity decreased at 0.1 and 1μgL(-1) and increased at 100μgL(-1) and lipoperoxidation increased in all tested concentrations. Fish exposed to 0.1, 1 and 100µgL(-1) Cd presented increase in hepatic lesion index. In the kidney, the catalase activity and LPO reduced in all exposed groups. The gluthatione peroxidase, etoxiresorufin-O-deethylase activities and metallothionein increased at the highest concentration of Cd, but the level of reduced glutathione decreased. The genotoxicity was observed at 0.1 and 100μgL(-1). Neurotoxicity was not observed. The results showed that low concentrations (range of μgL(-1)) of Cd caused hepato-, nephro- and hematological alterations in this freshwater fish species.

Extraction method for the determination of atrazine, deethylatrazine, and deisopropylatrazine in agricultural soil using factorial design

An optimization procedure for the extraction of the herbicide atrazine (AT), and the main degradation products deethylatrazine (DEA) and deisopropylatrazine (DIA) from an oxisol soil sample was carried out, for a soil from the Southwest of Parana State in Brazil, where AT is among the most largely employed herbicide. A comparison between shaking and ultrasound extraction was performed, to define a simple and fast extraction procedure, followed by the quantification using high performance liquid chromatography. It is important to inform that a factorial planning was employed, that was very important to define the best conditions of extraction by shaking. Appropriate recovery values were observed using soil samples from three different depths, as well as the relative standard deviation, suggesting the possibility to employ the proposed extraction method for quantification of AT, DEA and DIA in oxisol samples.

DIGESTÃO FOTOQUÍMICA, ASSISTIDA POR MICROONDAS, DE ÁGUAS NATURAIS: APLICAÇÃO EM ESTUDOS DE PARTIÇÃO E ESPECIAÇÃO DO COBRE

-1 humic acid solution after 15 min of UV irradiation. In the presence of H 2 O 2 , only 3 min were necessary to accomplish a reduction of almost 100% in the emission and 6 min to reduce the concentration of dissolved organic carbon by 95%. The copper recovery from synthetic samples containing commercial humic acid, from soil suspensions, as well as from natural waters varied between 91.5 and 106.6%. The digestion of dissolved and unfiltered samples was successfully accomplished in 6 and 12 min, respectively. No contaminations or sample losses were observed. Results of copper speciation in natural waters showed that this metal is predominantly bound to natural ligands. Only 3-6% of the total recoverable copper is present in the labile form.